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ENANTIOSELECTIVE BINDING IN GAS CHROMATOGRAPHY:A COMPUTATIONAL STUDY OF CHIRAL SELECTION BYPERMETHYL‐β‐CYCLODEXTRIN
Author(s) -
Lipkowitz Kenny B.,
Coner Bob,
Peterson Michael A.,
Morreale Antonio
Publication year - 1997
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199705)10:5<311::aid-poc871>3.0.co;2-p
Subject(s) - chemistry , van der waals force , intermolecular force , enantiomer , diastereomer , cyclodextrin , enantioselective synthesis , london dispersion force , computational chemistry , molecular dynamics , binding energy , polar , stereochemistry , organic chemistry , molecule , catalysis , physics , astronomy , nuclear physics
Stochastic molecular dynamics simulations were used to determine the enantiomer retention orders of moderately polar analytes binding to permethylated β‐cyclodextrin, a popular chiral stationary phase used in gas chromatography. It is found that averaging over multiple trajectories, each of which are lengthy, is required to faithfully reproduce experiment. From the simulations we find the major binding domain to be the interior of the macrocycle rather than the exterior with most analytes having a preference for associating to the primary rim rather than to the secondary rim. It is also found that the intermolecular forces responsible for holding the complexes together are the short range dispersion forces, and that the enantiodifferentiating forces of the competing diastereomeric complexes are dominated by the van der Waals contributions to the intermolecular energy. © 1997 John Wiley & Sons, Ltd.